Patented Oct. 15, 1946 ' UNU'ED 2,4t9,275 STATES PATENT OFFICE 2,409,275 CHEMICAL COIWPOUNDS AND METHOD OF PRODUCING SAME Benjamin B. Harris, Chicago, Ill. N0 Drawing. Application May 19, 1944, Serial No. 536,432 16 Claims. 1 This invention relates to the preparation of new and useful water-soluble or water-dispersihle chemical compounds which are characterized by possessing interface modifying properties render‘ ingr the same highly useful for the purposes here inafter set forth. In general, the new and useful compounds and reaction products of the present invention are most, suitably prepared by reacting an anhydride of a lower molecular weight carboxylic acid ester of a hydroxypolycarboxylic acid with a carboxyl ic acid partial amide of a polyamine, particularly , an alkylene polyamine, the carboxylic acid radical of which amide contains preferably at least four carbon atoms and especially from eight to eight een carbon atoms. By way of illustration, this may be exempli?ed by reacting the anhydride of the acetic acid ester of citric acid with the lauric acid mono-amide of ethylene diamine. In addi tion to the novelty of the method, the reaction products produced herein have never been dis closed heretofore and, therefore, their utility for the purposes hereinafter described has been un known. While many of the novel products of the pres ent invention may best be de?ned in the form of reaction products, they and particularly some of the more potent constituents thereof can, at least in part, be characterized or described by way of structural formulae. Illustrative examples of such compounds which fall within the scope of the invention are as follows: 0 O 0- CH: l\OOONa » Hr-COONa (10) 2,409,275 3 In order that the full signi?cance of the inven tion may be even more apparent, the following illustrative examples are set forth. It will be ap preciated that the proportions of reacting ingre dients, times of reaction, temperatures of reac 4 tralized in whole or in part, and may be treated, if desired, to recover the compound in pure or substantially pure form. The hydroxy polycarboxylic acid anhydrides GI tion, and the like may be varied and that sup whose acetic acid esters and similar derivatives are reacted with the esters, in accordance with the present invention, may be selected from a large group including, for example, citric acid, plementary process of puri?cation and the like may be resorted to wherever-found ‘desirable or tartaric acid, malic acid, hydroxy methylsuccinic convenient. These and other variations and 10 acid, trihydroxyglutaric acid, mucic acid, sac modi?cations will be evident to those skilled in charic acid, and the mono- and poly-hydroxy de the art in the light of the guiding principles rivatives of adipic acid, pimelic acid, suberic acid, which are disclosed herein. ‘ ‘ ' Example A 24 parts of weight of the lauric acid mono amide of ethylene diamine and 23 parts by weight of the anhydride of the O-O-diacetic acid ester, of tartaric acid anhydride are heated at about azelaic acid, sebacic acid, and the like. 1 It is pre ferred to employ the anhydrides of the acetic acid esters or like esters of those hydroxy polycar boxylic acids which are water-soluble and of ali phatic character. These acids may contain other substituents such as CN, NI-Iz, N02, F, Cl, Br, I, SOsI-I, phosphate, sulphate, SCN, etc., but, for 100° C. to 115° C. until a homogeneous product is obtained. The resulting reaction product con 20 best results, substituents should be absent. Of particular importance are citric and tartaric tains a substantial amount of a compound of acids. the formula In place of the anhydrides of the acetic acid "esters of the hydroxy polycarboxylic acids, there may be employed the anhydrides of any carbox ylic acid ester of a hydroxy polycarboxylic acid, said carboxylic acid being preferably water-solu ble and of aliphatic or fatty character and par ticularly containing not more than six carbon The product may be partially or completely neu-.I 30 atoms although the invention is not so limited. Examples of such derivatives are those from pro tralized with any of the alkaline materials men Vpionic acid, butyric acid, valeric acid, maleic acid, tioned hereafter. It shows good foaming and succinic acid, and the like. or particular utility, wetting-out characteristics. The reaction mix however, are the acetic acid ester derivatives. ture may, if desired, be treated to recover the desired compound therefrom by means of organic. 35 The partial amides which are reacted with the anhydrides of the acetic acid esters of the hy solvents. Alternatively, if desired, the reaction droxy polycarboxylic acids may be derived from mixture may be evaporated to dryness, preferably a large group of carboxylic acids and polyamines. in vacuo, and used as such or the desired com Representative of such partial amides are, for pound recovered therefrom by means of organic example, including some of those set out herein solvent media. above, the lauric acid mono-amide of ethylene di Example B . amine, the oleic acid mono-amide of ethylene di 34 parts by weight of the palrnitic acid mono amine, the lauric and oleic acid mono-amides of amide of diethylene triamine and 23 parts by diethylene triamine, the caprylic acid mono weight of the anhydride of the acetic acid ester 45 amide of triethylene tetra-amine, the ricinoleic about 100° C. to 120“ of citric acid are heated at acid mono-amide of propylene diamine, and the C. until a homogeneous product is obtained. The like. resulting product contains a substantial amount A representative list of carboxylic acids the of acompound of the formula partial amides of which with the polyamines are 50 utilized in accordance with the present invention comprises straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic (including cycloaliphatic), fatty, aromatic, hy dro-aromatic, and araliphatic acids including The reaction product, which had properties simi 55 acetic acid, propionic acid, butyric acid, caproic acid, pimelic acid, enanthic acid, caprylic acid, lar to those of Example A, may be neutralized pelargonicv acid, capric acid, sebacic acid, behenic in whole'or in part, and may be treated, if de acid, arachidic acid, cerotic acid, erucic acid, me sired, to recover the compound in pure or sub lissic acid, stearic acid, oleic acid, ricinoleic acid, stantially pure form. too ricinelaidic acid, ricinostearolic acid, linoleic acid, Example C linolenic acid, lauric acid, myristic acid, palmitic 32 parts by weight of the oleic acid mono amide of ethylene diamine and 26 parts by weight of the ‘anhydride of the propionic acid ester of citric acid are heated at about 100° C. to 120°~' 65 C. until a homogeneous product is obtained. The resulting reaction product contains a substantial amount of a compound of the formula The reaction product, which has properties simi lar to those of Examples A and B, may be neu acid, mixtures of any two or more of the above mentionedv acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soya bean oil, peanut oil, castor oil, seal oils, whale oil, shark oil and other ?sh oils, partially or com-. 70 plete hydrogenated animal and vegetable oils such as those mentioned; oxidized hydroxy and alpha hydroxy higher carboxylic, aliphatic and fatty and/or polymerized higher fatty acids or higher fatty acids derived from oxidized and/0r polymer ized triglyceride oils; acyloxy carboxylic acids 2,409,275 5 6 amino-propanol; alkylamines such as ethylamine, as i-hydroxy stearic acid, dihydroxypalmitic acid, - di-hydroxy-stearic acid, dihydroxybehenic acid, alpha-hydroxy capric acid, alpha-hydroxy stear ic acid, alpha-hydroxy palmitic acid, alpha-hy droxy lauric vacid, alpha-hydroxy myristic acid, alpha-hydroxy coconut oil mixed fatty acids, a1 pha-hydroxy margaric acid, alpha-hydroxy ara C1 propylamine, laurylamine, cetylamine, butyl amine, hexylamine, cyclohexylamine, aniline, toluidines, dimethylamine, diethylamine, N methyl-N-ethyl amine, triethylamine, trimethyl amine, ethylene diamine, diethylene triamine, tri ethylene tetra-amine, betaine, mono-methyl ethylene diamine, monoethyl diethylene tetra amine, mono-allyl amine, hydrazine and substi tuted hydrazine, aromatic and heterocyclic bases chidic acid, and the like; fatty and similar acids derived from various waxes such as beeswax, spermaceti, montan wax, coccerin, and carnauba Wax and higher molecular weight carboxylic acids derived, by oxidation and other methods, from para?in wax, petroleum and similar hydro~ and cyclic nitrogenous substances such as ben zylamine, cyclohexylethyl aniline, morpholine, pyridine, dimethylaniline, N-methyi-N-benzyl‘ amine, N-ethyl-N-naphthyl amine, quinoline, carbons; resinic and hydroaromatic acids such as 15 quinaldine, piperidine, alkyl pyridines such as hexahydrobenzoic acid, naphthenic acid and abietic acid; araliphatic and aromatic acids such methylpyridine, pyrrolidines, nicotine, and homo as phthalic acid, benzoic acid, Twitchell fatty acids, naphthoic acid, pyridine carboxylic acid; hydroxy aromatic acids such as salicylic acid, hy droxy benzoic and .naphthoic acids, and the like. thereof, and, in general, primary, secondary and logues and derivatives or substitution products tertiary amines substituted or not with other rad icals, such as hydroxy, alkyl, aryl, cycloalkyl groups and the like; ' quaternary ammonium bases or hydroxides such as tetra-methyl ammo It Will be understood that mixtures of any two or more of said acids may be employed if desired and it will also be appreciated that said acids may contain substituent groups such as sulphate, sul nium hydroxide, tetra-ethyl ammonium hydrox ide, quaternary ammonium bases with dissimilar alkyl radicals such as methyl-triethyl ammonium hydroxide, propyl trimethyl ammonium hydrox phonic, nitrile, cyanogen, carbonyl, amide, amine, vhalogen, ketone and other groups. Of particular utility are the unsubstituted fatty acids contain ing from twelve to eighteen carbon atoms. The polyamines the partial amides of which are employed in the reactions may be selected from a large group, particularly the alkylene poly amines and polyalkylene polyamines and the alkyl and aralkyl derivatives thereof, as for example, ide; mixtures of any two or more of said bases as, for example, in the case of commercial triethanol amine which contains minor proportions of mono and di-ethanolamine; proteins and partial di gestion or hydrolysis products thereof. It will be understood that these substituted ammonium compounds or organic nitrogenous bases may be utilized in pure, impure, or commercial form. It will be understood that by the term “cation,” as used throughout the speci?cation and claims, ethylene diamine, diethylene triamine, triethyl ene tetra-amine, propylene diamine, butylene di amine, dipropylene triamine, mono-ethyl ethyl is meant hydrogen and such other elements as are ene diamine, mono-ethyl diethylene tetra-amine, piperazine, mono-ethyl ethylene diamine mono ethyl diethylene triamine, beta-dimethyl-amino ethyl amine, and the like. It will be understood that partial amides of any of the listed carboxylic acids with any of the listed polyamines may be utilized for reaction in accordance with the invention. > The reaction products may be used as such or mentioned herein, and, in general, atoms or radi cals which are regarded as hearing a positive 40 charge or capable of replacing acidic hydrogen. The reaction products may be neutralized to methyl orange, litmus or phenolphthalein or to any desired hydrogen ion concentration. As a general rule, if the salts of the reaction products ' are employed, it is preferred to use the sodium, potassium, ammonium, alkylolamine, or other soluble salts. suitable anti-acid materials. In this connection, The compounds of the invention have utility in considerable latitude and modi?cation may be various arts in which interface modifying agents exercised. In general, inorganic as well as or 50 are employed. Many of them are fairly resistant ganic anti-acid agents may be employed. Exam to precipitation by calcium and magnesium salts ples of such agents which may be used satisfac and are compatible with acid and alkali media. torily are bicarbonates of the alkali metals, po They may be utilized in Washing and laundering tassiiun hydroxide, potassium carbonate, metal and in the textile and related industries wherein lic sodium, sodium hydroxide, sodium oxide, so 55 they function for wetting, lathering, detergent, dium carbonate, ammonium hydroxide, ammonia emulsifying, penetrating, dispersing, frothing and they may be neutralized, in whole or in part, with gas, calcium‘, magnesium, ammonium, and zinc oxides, hydroxides, and salts, potassium stearate, sodium stearate, and the like; organic nitrogenous foaming purposes. The textiles, various treat~ ments of which in the presence of the agents of the present invention is rendered effective, com bases such as primary, secondary and tertiary 60 prise natural products such as cotton, wool, linen amines including alcohol-, alkylol-, and aral and the like as well as the arti?cially produced kylol-amines, including monoethanolamine, di ethanolamine, triethanolamine, propanolamines, butanolamines, pentanolamines, hexanolamines, glycerolamines, sugar alkylolamines and sugar al cohol alkylolamines such as those of dextrose, sucrose, sorbitol, mannitol and the like; dimethyl monoethanolamine, diethyl monoethanolamine, dibutyl mono-ethanolamine, diethanol methyl amine, diethanol ethyl amine, diethanol butanol amine, cyclohexyl ethanolamine, diethanol cyclo hexylamine, ethanol aniline, alkylol polyamines such as alkylol derivatives of ethylene diamine, mono-methyl mono-ethanolamine, diethyl mono etha-nolamine; l-amino-Z, 3-propanediol; 1,2-di ?bres (and fabrics) such as rayon, cellulose, ace tates, cellulose ethers and similar arti?cial silk fabrics. ,It will be understood, of course, that the agents may be used in aqueous and other media either alone or in combination with other suitable salts of organic or inorganic character or with other interface modifying agents. In the dyeing of textiles many of them may be employed as as sistants in order to bring about even level shades. Many of them also may be used in the leather in dustry as wetting agents in soaking, dyeing, tan ning and the softening and other treating baths for hides and skins. Their utility as emulsifying 75 agents enables them to be employed for the prepa 2,409,275 7 ration of emulsions which may be used for in secticidal, fungicidal and for similar agriculture purposes. They have utility in the preparation of hair washes. and hair shampoos, dentri?ces of liquid, cream and powder type, cosmetic creams such as cold creams, vanishing creams, tissue creams, shaving creams of .the brushless and lathering type and similar cosmetic preparations. um sulphate, and the like; higher molecular weight sulphonic acid derivatives such as cetyl sodium sulphonate and lauryl sodium sulphonate; sulphocarboxylic acid esters of higher molecular weight alcohols such as lauryl sodium sulphoace tate, dioctyl sodium sulpho-succinate, dilauryl potassium sulpho-glutarate, lauryl monoethanol amine sulpho-acetate, and the like; higher fatty acid partial esters of aliphatic polyhydric alco Another use to which many of the agents of my invention may be placed is for the treatment of 10 hols, such as monolaurin, mono-olein, monoste arin, dilaurin, lauric acid mono-ester of ethylene paper or paper pulp or the like. Their capillary glycol 0r diethylene glycol, stearic and oleic acid or interfacial tension reducing properties en partial esters of polyglycerols, and the like; sul ables them to be employed in the fruit and vege phuric and sulphonic derivatives of condensation table industry in order to effect the removal from products of alkylolamines and higher fatty acids; fruits and the like of arsenical and similar sprays. . reaction products of phosphoric, pyrophosphoric, They possess utility in the ore dressing industry meta-phosphoric tetraphosphoric, and polyphos wherein they function effectively in froth ?ota tion and agglomeration processes. Their inter face modifying properties also permit their use in lubricating oils and the like enabling the-pro duction of effective boring oils, cutting oils, drill ing oils, wire drawing oils, extreme pressure lubri phoric acids with higher molecular weight alco hols; Turkey-Red oils; compounds of the type of isopropyl naphthalene sodium sulphonate, and them useful in various environments such as not be utilized in the pure state. Indeed, in most instances it will be found to be more convenient and commercially desirable to employ them in other classes of wetting agents, such as cationic agents, for example, lauryl amine and lauryl amine hydrochloride, lauryl pyridinium chloride, cants and the like. Various of them possess bac octadecyl pyridinium iodide, quaternary ammoni tericidal, germicidal, bacteriostatic, antiseptic, disinfectant, fungicidal, preserving and, in gen 25 um compounds generally, and the like. It will be understood that the compounds need eral, chemotherapeutic properties which render tooth pastes, tooth powders, liquid dentifrices, mouth washes and the like. Many of them may also be used with effect in the preparation of metal and furniture polishes, shoe polishes, in rubber compositions, for breaking or demulsify ing petroleum emulsions such as those of the Water-in-oil type which are encountered in oil the form of their reaction mixtures with or with out the addition of diluents. It will also be un derstood that mixtures of any one or more of the reacting constituents may be employed in pro ducing the products hereof and this is particu.. ?eld operations, in paints and the like, and for 35 larly the case where commercial supplies of the chemicals are utilized; and, in addition, any of various other purposes which will readily occur the esters of the hydroxy polycarboxylic acid an to those versed in the art in the light of my dis hydrides listed above may be reacted with any closure herein. of the partial amides of the polyamines described. As detergents, they may in general be dissolved in water or aqueous media and utilized inthat form or, in the case of solid products, they may The term “higher,” as used herein and in the claims to describe carboxylic and fatty acids and the like, will be understood to mean at least eight be packaged and sold in such form preferably carbon atoms unless otherwise speci?cally stated. mixed with diluents. They may also be utilized The term “poly” wherever used herein will be for commercial cleansing, 1aundering and wash 45 understood to be employed in its usual sense, ing operations with advantage. namely, to denote two or more. It will be understood that the products of the What I claim as new and desire to protect by present invention may be employed for their var Letters Patent of the United States is: ious purposes either alone or together with lesser 1. A process of preparing new chemical com .or greater quantities of inorganic or organic com pounds. Thus, for example, many of them may 50 pounds which comprises condensing a carboxylic acid mono-amide of a polyamine with an anhy be employed together with salts such as sodium dride of an aliphatic carboxylic acid ester of an chloride, alkali metal phosphates including pyro phosphates and tetraphosphates, sodium sul phate, alums, perborates such as sodium perbo rate, and the like. aliphatic hydroxy-polycarboxylic acid, the radi cal of said last-mentioned aliphatic carboxylic Many of said products may 55 acid containing less than 6 carbon atoms, to be utilized in alkaline or acid media in the pres ence ofsodium carbonate, sodium bicarbonate, dilute acids such as hydrochloric, sulphurous, acetic and similar inorganic and organic acids. They may also be employed in the presence of such diverse substances as hydrophilic gums in cluding pectin, tragacanth, karaya, locust bean, gelatin, arabic and the like, glue, vegetable, ani mal, ?sh and mineral oils, solvents such as car amidify the mono-amide of the polyamine through a carboxyl group of said polycarboxylic acid anhydride. 2. A process of preparing new chemical com pounds which comprises condensing a fatty acid mono-amide of an alkylene polyamine, the fatty acid radical of which contains at least 6 carbon atoms, with an anhydride of a lower molecular weight fatty acid ester of a water-soluble ali bon tetrachloride, monoethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, mono ethyl and monobutyl ethers of diethylene glycol, cyclohexanol, and the like.‘ They may be used phatic hydroxy-dicarboxylic acid, the lower mo lecular weight fatty acid radical of which con tains less than 6 carbon atoms, to amidify the mono-amide of the alkylene polyamine through together with wetting, emulsifying, 'frothing, foaming, penetrating or detergent agents such hydride. , as the higher molecular weight alkyl sulphates‘, phosphates, pyrophosphates, and tetraphos phates as, for example, lauryl sodium sulphate, myristyl sodium pyrophosphate, cetyl sodium tetraphosphate, octyl sodium sulphate, oleyl sodi a carboxyl group of said dicarboxylic acid an 3. A process of preparing new chemical com pounds which comprises condensing the lauric acid mono-amide of an alkylene diamine with an anhydride of a lower molecular weight aliphatic monocarboxylic acid mono-ester of a water-solu; 2,409,275 ' 10 9 ble aliphatic hydroxy-polycarboxylic acid, the lower molecular weight aliphatic monocarboxylic acid radical of which contains less than 6 carbon atoms, to amidify the mono-amide of the alkylene diamine through a carboxyl group of said poly carboxylic acid anhydride. 4. A process of preparing new chemical com pounds which comprises condensing a fatty acid mono-amide of an ethylene polyamine, the fatty acid radical of which contains from 8 to 18 car bon atoms, with an anhydride of a water-solu ble acetic acid ester of an aliphatic hydrdxy alkylene polyamines, the fatty acid radical of which contains from 8 to 18 carbon atoms. 11. Amides of polyamines containing at least 2 primary amino groups, one of said primary amino groups being amidi?ed with a carboxylic acid containing at least 6 carbon atoms in a straight chain, and one of said primary amino groups be amidified by a lower molecular weight ali phatic carboxylic acid ester of a hydroxy-poly 10 carboxylic acid through a carboxyl group of the polycarboxylic acid, to amidify the mono-amide hydroxy-polycarboxylic acid, the lower molecu lar weight aliphatic carboxylic acid radical of said ester containing less than 6 carbon atoms. of an ethylene polyamine through a carboxyl 12. Amides of ethylene diamine wherein one group of said polycarboxylic acid anhydride. 15 amino group of the ethylene diamine is amidi?ed 5. From water-soluble to water-dispersible ali with a fatty acid containing from 8 to 18 carbon phatic carboxylic acid esters of aliphatic hy atoms, and the other amino group of the ethyl droxy-polycarboxylic acids, the aliphatic carbox ene diamine is amidi?ed by the acetic acid ester ylic acid radical of Which contains less than 6 of tartaric acid through a carboxyl group of the carbon atoms, at least one carboxyl group of said 20 tartaric acid. hydroxy-polycarboxylic acid being amide-linked to a carboxylic acid amide of a polyamine con 13. The acetic acid ester of citric acid at least’ one carboxyl group of which is amide-linked to taining at least one free primary amino group, a carboxylic acid amide of a polyamine, and salts said amide-linkage occurring through said pri thereof. mary amino group of said carboxylic acid amide 25 14. The acetic acid ester of citric acid at least of a polyamine. ' one carboxyl group of which is amide-linked to 6. From water-soluble to water-dispersible fat_ the lauric acid mono-amide of ethylene diamine, ty acid esters of aliphatic hydroxy-polycarbox and salts thereof. ylic acids, the fatty acid radical of which con 15. Chemical compounds in accordance with tains less than 6 carbon atoms, at least one car 30 the formula ‘ boxyl group of said hydroxy-polycarboxylic acid being amide-linked to a carboxylic acid amide of an alkylene polyamine containing at least one free primary amino group, said amide-linkage occurring through said primary amino group of 35 said carboxylic acid amide of an alkylene poly amine. 7. From water-soluble to water-dispersible ali phatic carboxylic acid esters of aliphatic hy droxy-polycarboxylic acids, the aliphatic carbox 40 ylic acid radical of which contains less than 6 carbon atoms, at least one carboxyl group of said hydroxy-polycarboxylic acid being amide-linked to a fatty acid mono-amide of an alkylene dia mine, the fatty acid radical containing from 8 45 is a fatty acid acyl radical containing from 8 to ‘ 18 carbon atoms, alk is alkylene, M is a cation, 8. From water-soluble to water-dispersible and '0 is an integer from 1 to 3. acetic acid esters of aliphatic hydroxypolycarbox to 18 carbon atoms. ylic acids, at least one carboxyl group of said hy- 7 droxy-polycarboxylic acid being amide-linked to 16. Chemical compounds in accordance with the formula 0 a fatty acid mono-amide of an ethylene polya rnine, the fatty acid radical of said mono-amide containing at least 8 carbon atoms. 9. From water-soluble to water-dispersible acetic acid esters of water-soluble hydroxy-poly carboxylic acids, at least one carboxyl group of ‘said hydroxypolycarboxylic acids being amide linked to a fatty acid mono-amide of ethylene di amine, the fatty acid radical of said mono-amide containing at least 8 carbon atoms. 60 CH3 +=<> CH3 Where R-o t 10. Amides of lower molecular weight aliphatic carboxylic acid esters of aliphatic hydroxy poly is a fatty acid acyl radical containing from 8 to carboxylic acids, the lower molecular weight ali l8_carbon atoms, and M is a cation. phatic carboxylic acid radical containing less than 6 carbon atoms, with fatty acid amides of 65 BENJAMIN R. HARRIS.